Structural and spectroscopic characteristics of α-cyano-substituted α-phosphoryl(thiophosphoryl)acetonates in neutral chelate-bridged complexes. Crystal structure of [Cu[(PrO)2P(O)C(CN)C(Me)O]2]

A comparative study of the three-dimensional and electronic structures of the chelate salts (ML _n ) of enol forms of -cyano-substituted -phosphoryl- and -(thiophosphoryl)acetones (RO)₂P(X)C(CN)C=CMe(OH) (X = O or S; R = Pr or Et) with the Cu^I, Cu^II, and Co^II cations was carried out. In all complexes under consideration, the geometry of the central moiety of the O—C(Me)—C(CN)—P chelate-bridging ligand remains unchanged. The substantial electron delocalization involving the cyano group is observed in the O—C—C(CN)—P(X) ligand framework. The structure of the bis-chelate Cu[(PrO)₂P(O)C(CN)C(O)Me]₂ complex was established by X-ray diffraction analysis at 180 K and vibrational (IR and Raman) spectroscopy. The study in the temperature range from 290 to 140 K revealed the phase transition at 200 K accompanied by a change in the coordination polyhedron about the copper cation from a symmetrical octahedron (4+2 coordination) to a strongly unsymmetrically distorted octahedron (4+1+1 coordination). In both crystal modifications, four oxygen atoms form the base of the octahedron, and the axial positions are occupied by the nitrogen atoms.     

Crystal structure of Ir(III) complexes with 1,10-phenanthroline: K[Ir(phen)Cl4]·H2O and (Me4N)[Ir(phen)Cl4]

The crystal structure of two salts of the complex [Ir(phen)Cl₄]^? anion with K⁺ (K[Ir(phen)Cl₄]·H₂O, 1) and Me₄N⁺ ((Me₄N)[Ir(phen)Cl₄], 2) cations is determined. The iridium(III) ion is in a distorted octahedral environment consisting of chloride anions and a bidentate heterocyclic ligand of 1,10-phenanthroline (phen). A crucial role in the formation of the crystal structure of complex 1 belongs to K…Cl contacts, while in the crystal structure of complex 2, the stacking interactions dominate.     

Crystal structure of Co(III) α-dimethylglyoximates with imidazole

Two new dimethylglyoximate complexes [Co(DmgH)₂(Im)Cl] (I) and (ImH)[Co(DmgH₂)₂Cl₂] (II), where DmgH^? is the dimethylglyoxime residue and Im is the imidazole molecule, are synthesized. The composition and structure of the crystals are determined from the elemental analysis, IR spectra, and single crystal X-ray diffraction. Complex I is molecular, containing the Im molecule as a coordinated ligand; complex II is of the ionic type with (ImH)⁺ involved as an outer-sphere organic cation. The mode of component packing in the crystals mainly depends on the imidazole position in the compounds.     

Reactions of trans-[Pt(H2){P(C6H11)3}2] with heterocumulenes. The crystal and molecular structure of trans-[Pt{P(C6H11)3}2(H){OCHC(C6H5)2}]

Trans-PtH₂(PCy₃)₂ (1) reacts with phenylisocyanate (2) and with diphenylketene (3) to yield the formamido complex (4) and the vinyloxo complex (5), respectively. The structure of 5 has been determined by X-ray diffraction.     

Structurally different divalent metallasiloxanes [Mg{O(Ph2SiO)2}2]-μ-(LiPy)-μ-{(LiPy)3(OH)(Cl)}], [Cr{O(Ph2SiO)2}-μ-(LiPy2)2], and [{O(Ph2SiO)2}Co{O(Ph2SiO)3)}-μ-(LiPy2)2] from Ph2Si(OH)2/2BuLi and the metal dichlorides

Three structurally different metallasiloxanes were formed from reactions between in situ generated suspensions of Ph₂Si(OH)₂/BuLi (1∶2) in tetrahydrofuran (THF) with, metal dichlorides MgCl₂·2THF, CrCl₂, or CoCl₂ followed by toluene/Py (Py=pyridine) work-up. The X-ray structures are reported for: [Mg{O(Ph₂SiO)₂}₂]-μ-(LiPy)-μ-{(LiPy)₃(OH)(Cl)] (1) incorporating two six-membered magnesiasiloxane rings and an MgLi₃O₃Cl cubane fragment, [{O(Ph₂SiO)₂}Co{O(Ph₂SiO)₃}-μ-(LiPy₂)₂] (2) with both six-and eight-membered cobaltasiloxane rings and [Cr{O(Ph₂SiO)₂}₂-μ-(LiPy₂)₂] (3) with two six-membered chromiasiloxane rings. Structure assembly in these cases is apparently dictated by the metal dichloride. The compound [{O(Ph₂SiO)₂}Mg{O(Ph₂SiO)₃}-μ-(CoClPy)₂]·Py (4) is formed from [{O(Ph₂SiO)₂}Mg{O(Ph₂SiO)₃}-μ-(LiPy₂)₂] and CoCl₂ (1∶2).     

Crystal structure of [Co(NH3)5Cl]2(W10O32)·4H2O

By single crystal X-ray diffraction the crystal structure of the complex salt [Co(NH₃)₅Cl]₂(W₁₀O₃₂)·4H₂O is determined and the IR spectrum is interpreted. The crystal chemical analysis of the structure of complex cations and decatungstate anions and their packing in the structure is performed.     

Crystal structures of hafnium(IV) and zirconium(IV) complexes with β-diketones

Preparation methods are developed for a number of 7- and 8-coordinated derivatives of Hf(IV) and Zr(IV) with β-diketonate ligands (R¹-CO-CH-CO-R²). The complexes obtained are examined by IR spectroscopy, mass spectrometry, and X-ray crystallography. All structures are molecular. The M-O distances fall within 2.09–2.28 Å. In the crystals, the molecules are joined only by van der Waals interactions. It is demonstrated that the series of hafnium(IV) and zirconium(IV) chelates with identical ligands are isostructural, and the introduction of CF₃- or tert-butyl groups in the terminal positions of the ligand as well as chlorine substitution for one of the ligands do not essentially affect the basic geometric characteristics of the ligand in the complexes.     

Crystal structure of Ni(NCS)2 · 2Ph3P

Crystals of the complex Ni(NCS)₂ · 2Ph₃P are triclinic with a = 7.939(4) Å, b = 10.457(5) Å, c = 11.474(5) Å, α = 111.08(3)°, β = 74.56(3)° and γ = 92.25(3)°. X-ray data for 2692 independent observed reflections were collected and the structure determined by Fourier methods and refined to R = 0.038. The nickel geometry is square planar with the triphenylphosphine ligands occupying trans positions. A feature of the structure is the large value (173.3°) for the NiNC angles.     

Synthesis and Crystal Structure of K3[HO{VO(O2)2}2]·H2O

The title compound K3[HO{VO(O2)2}2]·H2O has been synthesized and its crystal structure was determined by X-ray diffraction method. The crystal is of monoclinic, space group P21/c with a = 6.7078(3), b = 9.9539(6), c = 15.8182(9)A, β = 93.702(3)0, V = 1053.96(10)A3, Mr = 414.20, Dc = 2.610 g/cm3, Z = 4, λ(MoKα) = 0.71073A, F(000) = 808, μ = 3.014 mm-1, the final R = 0.0173 and wR = 0.0466 for 2178 observed reflections with I > 2σ(I). X-ray diffraction reveals that the coordination polyhedra of V atoms are not chemically equivalent: the V(1) and V(2) polyhedra can be described as pentagonal pyramid and pentagonal bipyramid, respectively.     

Optically active pseudoctahedral rhodium(III), iridium(III), and ruthenium(II) complexes with α-amino acidato ligands. Crystal structures of RIrSCSN- and SIrSCSN-[(C5Me5)Ir(pro)Cl] · 12H2O (Hpro = l-proline)

The synthesis and characterization of optically active amino acidato complexes of the types [(C₅Me₅)M(aa)Cl], [(p-cymene)Ru(aa)Cl], [(C₅Me₅)M(aa)(PPh₃)]BF₄, and [(p-cymene)Ru(aa)(PPh₃)]BF₄ (M = Rh, Ir; Haa = l-alanine, l-proline), in which the metal is a chiral centre, are reported. The cationic species were prepared via the solvato-complexes [(C₅Me₅)M(aa)(MeOH)]⁺ and [(p-cymene)Ru(aa)(MeOH)]⁺, which epimerize rapidly on the ¹H NMR time scale. The crystal structure of the complex [(C₅Me₅)Ir(pro)Cl] is reported; the asymmetric unit contains two independent molecules differing in the configuration at the metal.     

Crystal structure and thermal properties of [Pt(NH3)5Cl][ReCl6]Cl·H2O

The crystal structure of double complex salt [Pt(NH₃)₅Cl][ReCl₆]Cl·H₂O is determined. Crystallographic characteristics are: a = 23.9502(4) Å, b = 7.5963(1) Å, c = 8.9016(2) Å, V = 1619.49(5) ų, space group Pnma, Z = 4, d _x = 3.150 g/cm³. The packing of structural fragments is studied. It is shown that on heating the salt in a helium atmosphere up to 840 °C a mixture of two solid solutions of fcc Pt_0.90Re_0.10 and hcp Pt_0.25Re_0.75 forms.     

Structural and thermal study of asymmetric α-dioxime complexes of Co(III) with Cl and methyl-pyridines

Two new cobalt(III)-chelates, trans-bis(methyl-ethyl-dioximato)-chloro-β-picoline-cobalt (III) (1), and trans-bis(methyl-ethyl-dioximato)-chloro-3,4-lutidine-cobalt (III) (2) were obtained by oxidizing a mixture of CoCl₂, methyl-ethyl-dioxime and amines: β-picoline (3-methyl-pyridine) for (1) and 3,4-lutidine (3,4-dimethyl-pyridine) for (2). The crystal structure of (1) was determined by single crystal XRD (monoclinic, space group P2₁/c (No. 14) with a = 8.391(3) Å, b = 14.421(5) Å, c = 18.383(8) Å, β = 114.57(2)°, R = 0.0499), while both (1) and (2) were studied by middle and far FTIR spectroscopy, electrospray ionization (ESI) MS, powder XRD and thermal analysis (TG/DTA-MS). Melting of the related complexes 1 and 2 at 219 and 184 °C, respectively, results in an immediate chemical degradation of their whole structure and tarring of ligands.     

Synthesis and structure of bismuth complexes [Ph3MeP] 2 + [BiI3.5Br1.5(C5H5N)]2− · C5H5N, [Ph4Bi] 4 + [Bi4I16]4− · 2Me2C=O, and [Ph3(iso-Am)P] 4 + [Bi8I28]4− · 2Me2C=O

Complexes [Ph₃MeP] ₂ ⁺ [BiI_3.5Br_1.5(C₅H₅N)]^2? · C₅H₅N(I), [Ph₄Bi] ₄ ⁺ [Bi₄I₁₆]^4? · 2Me₂C=O (II), and [Ph₃(iso-Am)P] ₄ ⁺ [Bi₈I₂₈]^4? · 2Me₂C=O (III) were synthesized by reactions of bismuth iodide with triphenylmethylphosphonium bromide, triphenylbismuthonium sulfosalicylate, and triphenylisoamylphosphonium iodide, respectively. The crystal structures of complexes I–III were determined by X-ray crystallography. The complexes contain, in addition to cations and solvent molecules, mono-, tetra-, and octanuclear anions, in which bismuth atoms are in octahedral coordination.     

Crystal structure of bis[Ba(Aet)(OH2)5]bis(Aet)·4H2O

An X-ray crystallographic study is conducted of single crystals with the composition [Ba₂(Aet^?)₂·10(H₂O)]²⁺·2(Aet^?)·4H₂O, where Aet^? = (C₁₀H₁₁N₄O₂S₂)^? is the ethazole (2-(para-aminobenzenesulfamido)-5-ethyl-1,3,4-tiadiazole) anion. The crystals are monoclinic; the space group is P2₁/c, Z = 2; a = 9.793(2) Å, b = 15.408(4) Å, and c = 22.553(6) Å; β = 94.98(2)°; and R = 0.047. The independent part of the compound’s structural formula, [Ba(Aet)(OH₂)₅](Aet)·2H₂O, is isostructural with the analogous compound with the Sr atom. The ethazole anion is coordinated to the complexing metal atom by oxygen and nitrogen atoms to form a four-membered ring.     

Theoretical Study of Reactions of α-Diimines with P(III) Acid Halides by Semiempirical Quantum-Chemical Methods

Stability of potential products of -diimine reactions with P(III) acid halides was characterized by PM3 semiempirical quantum-chemical calculations with full geometry optimization. The energetic favorability of formation of diazaphospholene (oxodiazaphospholene) or diazaphospholane cyclic structures with an exocyclic diene system from acyclic diimines and cyclohexanediimine and the unfavorability of formation of similar structures from dihydropyrazines was demonstrated. Dihydropyrazines should prefer phosphorylation involving one of the C = N bond. The calculation results fairly agree with available experimental data and allow prognosis of the probability of formation of one or another structure in new reactions.     

Bis(citrato)germanate complexes with organic cations: Crystal structure of (HNic)2[Ge(HCit)2]·3H2O

Bis(citrato)germanate complexes with organic cations—protonated nicotinic acid ((HNic)₂[Ge(HCit)₂]·3H₂O (I)), protonated nicotinamide ((HNad)₂[Ge(HCit)₂]·3H₂O (II)), and protonated isonicotinic acid hydrazide ((HInd)₂[Ge(HCit)₂] (III)) (H₄Cit is citric acid)—have been synthesized for the first time. Complexes I–III were studied by chemical and X-ray powder diffraction methods, thermal analysis, and IR spectroscopy. The X-ray diffraction study of complex I was carried out. The crystals are monoclinic, a = 10.931(7) Å, b = 11.420(1) Å, c = 23.188(6) Å, β = 101.54(4)°, V = 2836(2) ų, z = 4, space group P2₁/n, R = 0.0334 for 1959 reflections with I > 2σ(I). In the complex anion [Ge(HCit)₂]^2? of the molecule of I, the coordination polyhedron of the Ge atom is a distorted octahedron formed by six O atoms of two tridentate chelating ligands HCit^3? (Ge-O, 1.806–1.957 Å). In the structure of I, anions, cations, and water molecules are linked together by an intricate system of hydrogen bonds.     

The synthesis of platinum and palladium cluster compounds with isocyanide or functionalised phosphine ligands. Crystal structures of [Pt5(CO)(μ-CO)5{Ph2PCH2C(O) Ph}4 and [Pt5(μ-CNC6H3Me2-2, 6)3(CNC6H3Me2-2, 6)5 {Ph2PCH2C(O) Ph}2]

The reaction of the ketophosphine ligand Ph₂PCH₂C(O)Ph (P～O) with [PtCl₂(NCMe)₂] and carbon monoxide in THF in the presence of an excess of zinc afforded the 70 electron pentanuclear cluster [Pt₅(CO)(μ-CO)₅(P～O)₄] (1). Reaction of the palladium(0) complex [Pd₂(dba)₃] CHCl₃ (dba = dibenzylideneacetone) with Ph₂PCH₂C(O)R [R = Ph or C₅H₄Fe(C₅H₅)] under SO₂ led to the pentapalladium cluster compounds [Pd₅(μ₃-SO₂)₂ (μ-SO₂)₂ {Ph₂PCH₂C(O)R}₅] (2a,R = Ph;2b,R = C₅H₄Fe(C₅H₅)), Cluster (1) reacts with 2,6-xylyl isocyanide, CNC₆H₃Me₂-2,6 to give a red cluster of formula [Pt₅(μ-CNC₆H₃Me₂-2, 6)₃ (CNC₆H₃Me₂-2, 6)₅ (P～O)₂] (3) and a green complex (4). The corresponding complexes (6) and (7) were also obtained by using PPh₃ instead of P～O. Clusters (2a) and (2b) react with [NEt₃Bz] Cl to give[NEt₃Bz][Pd₃(μ-SO₂)₂ (μ-Cl){Ph₂PCH₂C(O)R}₃](8a,R = Ph;8b,R = C₅H₄Fe(C₅H₅)). The molecular structures of (1) and (3) were determined by single-crystal X-ray diffraction analyses.